EP0277020B1 - Verfahren zur Herstellung eines supraleitenden Materials - Google Patents

Verfahren zur Herstellung eines supraleitenden Materials Download PDF

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Publication number
EP0277020B1
EP0277020B1 EP88300733A EP88300733A EP0277020B1 EP 0277020 B1 EP0277020 B1 EP 0277020B1 EP 88300733 A EP88300733 A EP 88300733A EP 88300733 A EP88300733 A EP 88300733A EP 0277020 B1 EP0277020 B1 EP 0277020B1
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EP
European Patent Office
Prior art keywords
compounds
superconductive
metal
metal oxide
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88300733A
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English (en)
French (fr)
Other versions
EP0277020A2 (de
EP0277020A3 (en
Inventor
Susumu Mizuta
Toshiya Kumagai
Wakichi Kondo
Kenji Kawaguchi
Shigemitsu Shin
Hiroshi Yokota
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National Institute of Advanced Industrial Science and Technology AIST
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Agency of Industrial Science and Technology
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Publication of EP0277020A3 publication Critical patent/EP0277020A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming superconductor layers
    • H10N60/0324—Processes for depositing or forming superconductor layers from a solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming superconductor layers
    • H10N60/0576—Processes for depositing or forming superconductor layers characterised by the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y10S505/734—From organometallic precursors, e.g. acetylacetonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y10S505/739—Molding, coating, shaping, or casting of superconducting material
    • Y10S505/741—Coating or casting onto a substrate, e.g. screen printing, tape casting

Definitions

  • This invention relates to a method of preparing a superconductive material.
  • the present invention provides a method of preparing a superconductive material having a superconductive metal oxide layer provided on a substrate, said method comprising the steps of:
  • the present invention provides a superconductive material including a substrate and a superconductive metal oxide layer provided over at least a portion of the surface of the substrate.
  • the superconductive material is produced by a method including the following steps.
  • the calcination temperature varies with the kind of the superconductive oxide, but generally in the range of 500-1000 °C.
  • the metal compounds are organic compounds, they are decomposed or oxidized at temperatures of 200-500 °C and crystallization or superconductive metal oxide forming reaction takes place at temperatures of 500-1000 °C.
  • Inorganic metal compounds such as metal nitrates, hydroxides, carbonates or halides are decomposed and oxidized to form superconductive metal oxides at temperatures of 1000 °C or below.
  • the calcination is preferably performed for 0.5 hour or more, more preferably 1-72 hours.
  • the calcination step and the above-described drying step may be conducted separately or continuously.
  • the atmosphere in which the calcination is performed may be, for example, air, oxygen, nitrogen or argon. Calcination in an oxygen-free atmosphere should be followed by calcination in oxygen-containing atmosphere at 500-1000 °C. In the calcination step, pressurized condition, ambient pressure or reduced pressure may be used.
  • the calcination product is then allowed to be cooled to room temperature to obtain a superconductive composite material having a superconductive metal oxide layer provided over the surface of the substrate.
  • the method of the present invention can form superconductive composite materials having a superconductive layer with a thickness of 0.01-20 »m, especially 0.1-10 »m.
  • the thickness of the superconductive layer may be controlled by adjusting the concentration of the metal compounds in the coating solution or by repeating the coating and calcination steps suitable times.
  • the method of the present invention is particularly suited for the production of superconductive materials having a superconductive layer of the following oxides.
  • the present invention is applicable to any other superconductive metal oxides.
  • AB2Cu3O 7+x (La 1-y Z y )2CuO 4-z In the above formulae:
  • the metal compounds shown above were mixed with each other and the mixture dissolved in the above solvent to give a coating solution having the total metal compounds concentration shown above and having the molar ratio of the metals as shown above.
  • the coating solution was applied on the substrate shown above by immersing the substrate in the coating solution and the coat was dried in the air. Then the substrate having the dried coat was calcined under the conditions shown above. The immersing, drying and calcining steps were repeated 10 times to give a superconductive material whose electrical resistivity was abruptly decreased at the temperature (on set) shown above and which exhibited perfect superconductivity at the temperature shown above.
  • the electrical conductivity was measured by the four termini method in which four spaced apart electrodes with about 2 mm distance were provided on the superconductive layer by coating a silver paste thereon.
  • Examples 2-17 were conducted to prepare various superconductive materials under conditions as summarized below. In each of Examples 2-17, the procedure including coating, drying and 1st stage calcination steps was repeated in the number indicated below. Thereafter, the 2nd stage calcination was performed in an oxygen-containing atmosphere. The calcined product was then gradually cooled to room temperature.

Claims (11)

  1. Verfahren zur Herstellung eines supraleitenden Materials, bei dem eine supraleitende Metalloxidschicht auf ein Substrat aufgebracht worden ist, wobei das Verfahren die folgenden Schritte umfaßt:
    (a) Zubereitung einer nichtwäßrigen Lösung, die bei einer Zusammensetzung, die der der Metalle im supraleitenden Metalloxid entspricht, eine Mischung von Metallverbindungen enthält, wobei die Metallverbindungen unter Salzen, Chelaten, Halogeniden, Hydroxiden, Peroxiden und Oxiden der Metalle auszuwählen sind;
    (b) Aufbringen der Lösung auf das Substrat zur Bildung eines Flüssigkeitsfilms;
    (c) Trocknen des Flüssigkeitsfilms und
    (d) Kalzinieren des getrockneten Films zur Umwandlung der Metallverbindungen in eine supraleitende Metalloxidschicht.
  2. Verfahren nach Anspruch 1, bei dem das Substrat die Form eines Drahts oder einer Platte aufweist.
  3. Verfahren nach Anspruch 1 oder 2, bei dem es sich bei den Metallverbindungen um Verbindungen handelt, die durch Kalzinierung bei 1 000 °C oder darunter Oxide bilden können.
  4. Verfahren nach Anspruch 3, bei dem es sich bei den Metallverbindungen um Naphthenate, Octylate, Caprylate, Stearate, Laureate, Butyrate, Propionate, Oxalate, Citrate, Lactate, Benzoate, Salicylate, Ethylendiamintetraacetate, Nitrate, Carbonate, Hydrochloride oder Acetylacetonate der Metalle handelt.
  5. Verfahren nach Anspruch 3 oder 4, bei dem der Schritt (d) bei einer Temperatur zwischen 500 und 1 000 °C durchgeführt wird.
  6. Verfahren nach Anspruch 5, bei dem der Schritt (d) in einer sauerstoffhaltigen Atmosphäre über einen Zeitraum von 0,5 Stunden oder mehr ausgeführt wird.
  7. Verfahren nach Anspruch 6, bei dem vor der Kalzinierung in der sauerstoffhaltigen Atmosphäre die Kalzinierung in einer sauerstofffreien Atmosphäre erfolgt.
  8. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Schritte (a) bis (d) so lange wiederholt werden, bis die supraleitende Schicht eine Dicke von 0,01-20 »m aufweist.
  9. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Lösung eine erste Verbindung, die unter Y-Verbindungen, La-Verbindungen, Nd-Verbindungen, Sm-Verbindungen, Eu-Verbindungen, Gd-Verbindungen, Dy-Verbindungen, Ho-Verbindungen, Er-Verbindungen, Yb-Verbindungen und Lu-Verbindungen und Gemischen davon ausgewählt wurde, sowie eine zweite Verbindung, die unter Ba-Verbindungen, Sr-Verbindungen und Ca-Verbindungen sowie Gemischen davon ausgewählt wurde, und eine Cu-Verbindung enthält, so daß das supraleitende Metalloxid die folgende Formel aufweist:

            AB₂Cu₃O7+x

    in der A für Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu oder ein Gemisch von zwei oder mehr dieser Komponenten, B für Ba, Sr, Ca oder ein Gemisch aus zwei oder mehr dieser Komponenten und x für eine Zahl steht, die größer als -1, jedoch kleiner als +1 ist.
  10. Verfahren nach einem der vorstehenden Ansprüche 1 bis 8, bei dem die Lösung eine La-Verbindung, eine unter Ba-Verbindungen, Sr-Verbindungen, Ca-Verbindungen und Gemischen davon ausgewählte Verbindung sowie eine Cu-Verbindung enthält, so daß das supraleitende Metalloxid die folgende Formel aufweist:

            (La1-yZy)₂CuO4-z

    in der Z für Ba, Sr, Ca oder ein Gemisch von zwei oder mehr dieser Komponenten steht und y größer als 0, jedoch nicht größer als 0,2 und z eine Zahl ist, die kleiner als 1, jedoch nicht kleiner als 0 ist.
  11. Verfahren nach einem der vorstehenden Ansprüche, bei dem das Substrat aus einem Metall, Metalloxid oder aus Keramik geformt wird.
EP88300733A 1987-01-30 1988-01-28 Verfahren zur Herstellung eines supraleitenden Materials Expired - Lifetime EP0277020B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP21128/87 1987-01-30
JP2112887 1987-01-30
JP115186/87 1987-05-12
JP11518687 1987-05-12

Publications (3)

Publication Number Publication Date
EP0277020A2 EP0277020A2 (de) 1988-08-03
EP0277020A3 EP0277020A3 (en) 1990-07-04
EP0277020B1 true EP0277020B1 (de) 1995-04-19

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EP88300733A Expired - Lifetime EP0277020B1 (de) 1987-01-30 1988-01-28 Verfahren zur Herstellung eines supraleitenden Materials

Country Status (4)

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US (1) US5039654A (de)
EP (1) EP0277020B1 (de)
KR (1) KR880009453A (de)
DE (1) DE3853594T2 (de)

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DE3872430T2 (de) * 1987-04-10 1992-12-03 American Telephone & Telegraph Verfahren zur herstellung einer schicht aus supraleitendem material.
AU607219B2 (en) * 1987-05-29 1991-02-28 Toray Industries, Inc. Method of forming superconductive thin films and solutions for forming the same
US5304536A (en) * 1987-06-09 1994-04-19 E. I. Du Pont De Nemours And Company Process for making superconductor powder
US4908346A (en) * 1987-07-01 1990-03-13 Eastman Kodak Company Crystalline rare earth alkaline earth copper oxide thick film circuit element with superconducting onset transition temperature in excess of 77%
CA1336948C (en) * 1988-08-31 1995-09-12 William L. Olson Thallium superconducting products and methods for their manufacture
US5071830A (en) * 1988-08-31 1991-12-10 Superconductor Technologies, Inc. Metalorganic deposition method for forming epitaxial thallium-based copper oxide superconducting films
JP3081212B2 (ja) * 1990-03-06 2000-08-28 日産自動車株式会社 部分クエン酸塩法による複合酸化物の合成方法
IT1248618B (it) * 1990-08-01 1995-01-21 Sviluppo Materiali Spa Dispositivo per la produzione in continuo di ceramiche superconduttrici
US5273776A (en) * 1991-12-06 1993-12-28 Mitsubishi Materials Corporation Method for forming thermistor thin film
US6174564B1 (en) 1991-12-13 2001-01-16 Symetrix Corporation Method of making metal polyoxyalkylated precursor solutions
DE4304679C2 (de) * 1992-02-17 1996-03-21 Mitsubishi Electric Corp Verfahren zur Herstellung einer dünnen dielektrischen Schicht eines Oxid-Systems unter Verwendung des CVD-Verfahrens
JP2976028B1 (ja) 1998-10-13 1999-11-10 工業技術院長 緻密でエピタキシャルな金属酸化物膜の製造方法と、その金属酸化物前駆体及びその製造方法
US6210752B1 (en) * 1999-03-24 2001-04-03 Sandia Corporation All-alkoxide synthesis of strontium-containing metal oxides
JP2001279239A (ja) * 2000-03-29 2001-10-10 Sumitomo Chem Co Ltd 発光素子用蛍光体の製造方法および蛍光体ペースト
US20020056401A1 (en) 2000-10-23 2002-05-16 Rupich Martin W. Precursor solutions and methods of using same
JP4135857B2 (ja) * 2001-03-27 2008-08-20 独立行政法人産業技術総合研究所 赤外線センサの製造方法
JP3548801B2 (ja) * 2001-03-27 2004-07-28 独立行政法人産業技術総合研究所 特定の金属種に特定の配位子を配位させた金属錯体を含む溶液組成物、希土類超電導膜製造用溶液組成物、特定金属錯体の非結晶固形物、特定の金属種に特定の配位子を配位させた金属錯体を含む溶液の製造方法、希土類超電導膜製造用溶液の製造方法、及び超電導薄膜の形成方法。
JP4050730B2 (ja) * 2004-07-30 2008-02-20 株式会社東芝 酸化物超電導体およびその製造方法
JP4258536B2 (ja) * 2006-08-11 2009-04-30 独立行政法人産業技術総合研究所 結晶化金属酸化物薄膜の製造方法
US20080044590A1 (en) * 2006-08-21 2008-02-21 National Institute Of Advanced Industrial Science And Technology Manufacturing Method of Phosphor Film
EP2511235B1 (de) 2009-12-09 2019-07-10 National Institute of Advanced Industrial Science And Technology Lösung zur formung eines supraleitenden seltenerdfilms und herstellungsverfahren dafür

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Also Published As

Publication number Publication date
US5039654A (en) 1991-08-13
EP0277020A2 (de) 1988-08-03
DE3853594T2 (de) 1995-08-31
KR880009453A (ko) 1988-09-15
EP0277020A3 (en) 1990-07-04
DE3853594D1 (de) 1995-05-24

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